CN114409936B - Preparation method of composite film added with argininized chitosan and zinc oxide nano particles - Google Patents
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Abstract
The invention discloses a preparation method of a composite film added with argininized chitosan and zinc oxide nano particles, and relates to the field of food packaging. The invention uses polyvinyl alcohol (PVA) as a matrix, uses arginine for modification of chitosan through amidation reaction to obtain Arginine Chitosan (ACS), uses ACS and zinc nitrate hexahydrate (ZnNO) 3 •6H 2 O) is used as a raw material to prepare ACS-ZnO by a coprecipitation method; finally, ACS and ACS-ZnO are blended and added into PVA matrix to prepare the composite film with synergistic antibacterial effect. The composite film prepared by the method has the advantages of good mechanical property, ultraviolet blocking property, lower water vapor transmittance, excellent antibacterial property and the like, and can be used as an antibacterial environment-friendly packaging material.
Description
Technical Field
The invention relates to a preparation method of a composite film added with argininized chitosan and zinc oxide nano particles. The invention belongs to the field of food packaging materials.
Background
Along with the development of technology and improvement of human production level, the number and variety of foods on dining tables of people are increasingly abundant, and along with the development, the fresh-keeping requirements of people on food packaging are also increasingly high. However, most of the food packages on the market at present are non-degradable petroleum-based plastic packages, which cause serious damage to the global environment. Polyvinyl alcohol (PVA) is a water-soluble vinyl polymer, has good mechanical properties, is nontoxic and degradable, and is expected to be a food packaging material accepted by the masses.
As a biodegradable natural polymer material, the chitosan has good film forming property, biocompatibility and antibacterial property. However, chitosan is limited to only being dissolved in an acidic solution, greatly limiting its application. Arginine is used as the only amino acid containing guanidine, the strong antibacterial function of guanidine can endow the modified chitosan with better antibacterial property, and in addition, the arginine modified chitosan can break the intermolecular hydrogen bond of the chitosan, so that the water solubility of the chitosan is improved, and the improvement of the metal cation chelating capacity of the chitosan is facilitated.
Zinc oxide (ZnO) has been widely used as a source of zinc in the fields of foods, cosmetics, medicines and biology. The nano zinc oxide has broad-spectrum antibacterial property and good ultraviolet shielding effect. The nano particles can be used as packing filler to obviously reduce the water vapor transmittance of the film and obviously improve the mechanical properties of the composite film.
Disclosure of Invention
The invention aims to provide a preparation method of a composite film added with argininized chitosan and zinc oxide nano particles, and the prepared composite antibacterial film has good mechanical property, ultraviolet barrier property, lower water vapor transmittance and excellent antibacterial property, and can be applied to the field of food packaging.
The invention uses polyvinyl alcohol (PVA) as a matrix, uses arginine for modification of chitosan through amidation reaction to obtain Arginine Chitosan (ACS), uses ACS and zinc nitrate hexahydrate (Zn (NO) 3 ) 2 •6H 2 O) is used as a raw material to prepare ACS-ZnO by a coprecipitation method; finally, ACS and ACS-ZnO are blended and added into PVA matrix to prepare the composite film with synergistic antibacterial effect.
The invention provides a preparation method of a composite film added with argininized chitosan and zinc oxide nano particles, which comprises the following steps:
(1) 1-2 g of chitosan is weighed and dissolved in 50-100 mL MES buffer solution (25 mM,4 < PH < 6), and the solution is stirred on a magnetic stirrer for 1h until the chitosan is completely dissolved, wherein the solution is in a transparent state;
(2) 1-3 g of arginine is weighed and dissolved in 50-100 mL of MES buffer solution, and the mixture is stirred on a magnetic stirrer for 5 min until the arginine is completely dissolved;
(3) Weighing 1-5 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC), adding 1-4 g of N-hydroxysuccinimide (NHS) into the arginine solution in the step (2), and stirring and activating for 2 hours on a magnetic stirrer to obtain an activated arginine solution;
(4) Dripping the arginine solution activated in the step (3) into chitosan solution, heating to 45 ℃ in a magnetic stirrer, stirring for 12-24 hours, dialyzing 3 d in deionized water after the reaction is finished, and freeze-drying 48 h to obtain Arginine Chitosan (ACS);
(5) Weighing 0.5-1 g of the arginate chitosan synthesized in the step (4), dissolving in deionized water, heating to 70 ℃ in a magnetic stirrer, and stirring for 0.5-1 h until the arginate chitosan is completely dissolved;
(6) Weighing 1-2 g Zn (NO) 3 ) 2 •6H 2 Adding O into the arginized chitosan water solution in the step (5) and stirring for 30 min;
(7) Dropwise adding 50-100 mL of 0.2M NaOH solution into the solution obtained in the step (6), and stirring for 2h;
(8) Centrifuging the stirred solution obtained in the step (7), washing with deionized water for 3 times, and drying 24 and h in a 50 ℃ oven to obtain ACS@ZnO nano particles;
(9) 1-5 g PVA is weighed and dissolved in 10-50 mL deionized water, and the solution is heated to 95 ℃ and stirred for 2h until the solution is transparent;
(10) Weighing 1-2 g of the arginate chitosan prepared in the step (4), dissolving in 100-200 mL of deionized water, and stirring for 30min at normal temperature until the arginate chitosan is dissolved;
(11) Dropwise adding the arginized chitosan aqueous solution in the step (10) into the PVA aqueous solution in the step (9), and stirring for 2h; the volume ratio of the PVA aqueous solution to the argininized chitosan aqueous solution is 1:1-4:1,
(12) Adding ACS@ZnO nano particles in the step (8) into the mixed aqueous solution prepared in the step (11), performing ultrasonic dispersion for 30min, and preparing a composite film by a tape casting method; the ACS@ZnO nano particles account for 1-5% of the mixed aqueous solution by mass percent.
Further, the stirring rate was 2000rpm.
Further, the power of the ultrasonic probe is 200-500W, the ultrasonic power is 3s, and the intermittent power is 2s.
The invention has the beneficial effects that:
according to the invention, argininized chitosan and nano zinc oxide are used as antibacterial agents, and when the content of nano zinc oxide is 3% compared with a PVA film, the inhibition rate of the film compounded with PVA on staphylococcus aureus and escherichia coli is over 70%. In addition, the mechanical property, ultraviolet blocking property and water contact angle of the composite film are correspondingly improved, and the water vapor transmittance is correspondingly reduced. The composite film prepared by the invention has great application potential and prospect in the field of food packaging.
Drawings
FIG. 1 is an X-ray diffraction pattern of arginate chitosan and arginate chitosan-ZnO nanoparticles prepared by the invention.
FIG. 2 is a scanning electron microscope image of the arginate chitosan-ZnO nanoparticle prepared by the invention.
FIG. 3 is a graph showing the comparison of UV blocking properties of a composite film prepared according to the present invention.
FIG. 4 is a graph showing the comparison of water contact angles of composite films prepared according to the present invention.
FIG. 5 is a graph showing the comparison of the inhibition rates of E.coli and Staphylococcus aureus by the composite film prepared according to the present invention.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1
A method for preparing a composite antibacterial packaging film by adding arginate chitosan and zinc oxide nano particles comprises the following specific steps:
weighing 1 g chitosan, dissolving in 100 mL MES buffer (25 mM, PH=5), stirring on a magnetic stirrer for 1h until the chitosan is completely dissolved, wherein the solution is in a transparent state;
weighing 2.06. 2.06 g arginine and dissolving in MES buffer of 50mL, stirring on a magnetic stirrer for 5 min to completely dissolve
3.4 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 2.04 g of N-hydroxysuccinimide (NHS) were weighed into the arginine solution and activated by stirring on a magnetic stirrer for 2h;
dripping the activated arginine solution into chitosan solution, heating to 45 ℃ in a magnetic stirrer, and stirring for 12h
Weighing 0.5g of arginate chitosan, dissolving in 50mL of deionized water, heating to 70 ℃ in a magnetic stirrer, and stirring for 1h until the arginate chitosan is completely dissolved;
1.487g Zn (NO) was weighed out 3 ) 2 •6H 2 Adding O into arginine solution, stirring for 30min, then dropwise adding 50mL of 0.2M NaOH solution, stirring for 2h, centrifuging, washing, and drying in a 50 ℃ oven for 24h to obtain zinc oxide nano particles;
weighing 10 g of PVA into 100 mL deionized water, heating to 95 ℃, and stirring for 2 hours until the PVA is completely dissolved;
weighing 0.5. 0.5g arginized chitosan into 50mL deionized water, and stirring for 30min until the chitosan is completely dissolved;
taking the PVA aqueous solution prepared in the step (7) as a matrix, taking the corresponding argininized chitosan solution in the step (8) and adding the argininized chitosan solution into the PVA aqueous solution according to the volume ratio (PVA aqueous solution: ACS aqueous solution) of 2:1, and stirring the mixed solution on a magnetic stirrer for 1h to be uniform
And (3) adding ACS@ZnO nano particles with the mass percentage of 1% in the step (7) into the mixed solution, performing ultrasonic dispersion for 30min, and preparing a composite film with different ACS@ZnO nano particle contents by a tape casting method.
Example 2
A method for preparing a composite antibacterial packaging film by adding arginate chitosan and zinc oxide nano particles comprises the following specific steps:
weighing 1 g chitosan, dissolving in 100 mL MES buffer (25 mM, PH=5), stirring on a magnetic stirrer for 1h until the chitosan is completely dissolved, wherein the solution is in a transparent state;
weighing 2.06. 2.06 g arginine and dissolving in MES buffer of 50mL, stirring on a magnetic stirrer for 5 min to completely dissolve
3.4 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 2.04 g of N-hydroxysuccinimide (NHS) were weighed into the arginine solution and activated by stirring on a magnetic stirrer for 2h;
dripping the activated arginine solution into chitosan solution, heating to 45 ℃ in a magnetic stirrer, and stirring for 12h
Weighing 0.5g of arginate chitosan, dissolving in 50mL of deionized water, heating to 70 ℃ in a magnetic stirrer, and stirring for 1h until the arginate chitosan is completely dissolved;
1.487g Zn (NO) was weighed out 3 ) 2 •6H 2 Adding O into arginine solution, stirring for 30min, then dropwise adding 50mL of 0.2M NaOH solution, stirring for 2h, centrifuging, washing, and drying in a 50 ℃ oven for 24h to obtain zinc oxide nano particles;
weighing 10 g of PVA into 100 mL deionized water, heating to 95 ℃, and stirring for 2 hours until the PVA is completely dissolved;
weighing 0.5. 0.5g arginized chitosan into 50mL deionized water, and stirring for 30min until the chitosan is completely dissolved;
taking the PVA aqueous solution prepared in the step (7) as a matrix, taking the corresponding argininized chitosan solution in the step (8) and adding the argininized chitosan solution into the PVA aqueous solution according to the volume ratio (PVA aqueous solution: ACS aqueous solution) of 2:1, and stirring the mixed solution on a magnetic stirrer for 1h to be uniform
And (3) adding ACS@ZnO nano particles with the mass percentage of 3% in the step (7) into the mixed solution, performing ultrasonic dispersion for 30min, and preparing a composite film with different ACS@ZnO nano particle contents by a tape casting method.
Example 3
A method for preparing a composite antibacterial packaging film by adding arginate chitosan and zinc oxide nano particles comprises the following specific steps:
weighing 1 g chitosan, dissolving in 100 mL MES buffer (25 mM, PH=5), stirring on a magnetic stirrer for 1h until the chitosan is completely dissolved, wherein the solution is in a transparent state;
weighing 2.06. 2.06 g arginine and dissolving in MES buffer of 50mL, stirring on a magnetic stirrer for 5 min to completely dissolve
3.4 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 2.04 g of N-hydroxysuccinimide (NHS) were weighed into the arginine solution and activated by stirring on a magnetic stirrer for 2h;
dripping the activated arginine solution into chitosan solution, heating to 45 ℃ in a magnetic stirrer, and stirring for 12h
Weighing 0.5g of arginate chitosan, dissolving in 50mL of deionized water, heating to 70 ℃ in a magnetic stirrer, and stirring for 1h until the arginate chitosan is completely dissolved;
1.487g Zn (NO) was weighed out 3 ) 2 •6H 2 Adding O into arginine solution, stirring for 30min, then dropwise adding 50mL of 0.2M NaOH solution, stirring for 2h, centrifuging, washing, and drying in a 50 ℃ oven for 24h to obtain zinc oxide nano particles;
weighing 10 g of PVA into 100 mL deionized water, heating to 95 ℃, and stirring for 2 hours until the PVA is completely dissolved;
weighing 0.5. 0.5g arginized chitosan into 50mL deionized water, and stirring for 30min until the chitosan is completely dissolved;
taking the PVA aqueous solution prepared in the step (7) as a matrix, taking the corresponding argininized chitosan solution in the step (8) and adding the argininized chitosan solution into the PVA aqueous solution according to the volume ratio (PVA aqueous solution: ACS aqueous solution) of 2:1, and stirring the mixed solution on a magnetic stirrer for 1h to be uniform
And (3) adding ACS@ZnO nano particles with the mass percentage of 5% in the step (7) into the mixed solution, performing ultrasonic dispersion for 30min, and preparing a composite film with different ACS@ZnO nano particle contents by a tape casting method.
Performance test:
(1) XRD test: diffraction peak analysis was performed on the synthesized ACS and acs@zno, see fig. 1.
FIG. 1 shows X-ray diffraction patterns of CS, ACS and ACS@ZnO and a ZnO standard XRD pattern, and it can be seen from the graph that the diffraction peak intensity near 20 degrees in the curve of ACS is obviously reduced compared with that of CS, because the introduction of arginine on the CS chain breaks the intermolecular hydrogen bond of CS, so that the crystallinity of the polymer is reduced. The diffraction peaks appearing in acs@zno are consistent with the standard card for ZnO, indicating the synthesis of ZnO in the composite. Diffraction peaks of the prepared ZnO nano particles are respectively at 31 degrees, 34 degrees, 36 degrees, 47 degrees, 56 degrees, 62 degrees and 67 degrees, corresponding to (100), (002), (101), (102), (110), (103) and (122) crystal faces of JCPDS card No 76-0704, all peaks are well matched with ZnO standard XRD patterns, the formation of ZnO is confirmed, and the formed ZnO is of a hexagonal wurtzite crystal structure. No impurity peaks were observed in the XRD patternThe ZnO prepared has high purity and Zn (OH) 2 Completely converted into ZnO. In addition, a decrease in diffraction intensity of the amorphous peak of acs@zno around 20 ° indicates that the introduction of ZnO can reduce crystallinity of ACS.
(2) SEM test: the morphology size analysis was performed on the synthesized acs@zno, see fig. 2.
Fig. 2 is an SEM image of acs@zno, and it can be seen from the figure that acs@zno particles have an approximately spherical morphology, an average particle diameter of about 300 nm, a rough particle surface, and flocculent organic matter on the surface, which is arginate chitosan.
Mechanical property test: the test was carried out according to ISO 527-3 at a speed of 50 mm/min, see Table 1. Water vapor transmission rate test: the test was performed according to ASTM E96-95, table 1.
TABLE 1
Table 1 shows the elongation at break, the breaking strength and the water vapor transmission rate of the composite film, and it is clear from table 1 that the composite film to which ACS was added had both improved breaking strength and elongation at break due to the interaction of intermolecular hydrogen bonds, compared with the PVA film. And as the content of ACS@ZnO nano particles increases, the breaking strength and the breaking elongation of the composite film are increased, which shows that the addition of ACS@ZnO can increase intermolecular interaction, and the agglomeration phenomenon can occur along with the increase of the content, so that the elongation of the composite film is reduced. In addition, PVA itself has very strong water absorption, whereas a simple PVA film has low water vapor transmission rate due to the strong water absorption, and as acs@zno is added, the water vapor transmission rate of the composite film is reduced, because dispersion of nanoparticles in the polymer matrix can reduce defects of the composite film, thereby reducing the water vapor transmission rate of the composite film.
(4) Light transmittance test: the wavelength range was 200-800 nm as measured by a UV-vis spectrophotometer, see fig. 3.
Fig. 3 shows the result of the transmittance test of the composite film, and it can be seen from the graph that the composite film added with acs@zno has lower transmittance in the ultraviolet range (200-400 nm) compared with PVA and PVA/ACS films, and the transmittance of the composite film correspondingly decreases as the acs@zno content increases. The change is that the PVA/ACS/ZnO composite film has good protection effect on ultraviolet light because ZnO has excellent ultraviolet absorption performance and light scattering property, and can be possibly used as an ultraviolet shielding material.
(5) Water contact angle test: the composite films were tested using a contact angle meter, see fig. 4.
Fig. 4 shows the water contact angle test results of the composite film, and it can be seen from the graph that the water contact angle of the PVA/ACS composite film is improved (55 °) compared with that of the PVA film, because a large amount of amino groups in ACS are combined with hydroxyl groups in PVA to form hydrogen bonds, the interface combination of the composite film is improved, and the surface of the composite film is more compact, so that the hydrophilicity of the composite film is weakened. The water contact angle of the PVA/ACS/ZnO composite film is respectively increased to 71 degrees, 74 degrees and 77 degrees along with the increase of the ACS@ZnO content. The results demonstrate that the distribution of acs@zno in the composite film can increase the surface energy of the system to prevent the distribution of water droplets on the surface of the composite film.
(6) Antibacterial activity test: the antibacterial activity of the composite membrane was evaluated by colony counting, and the experimental strains were staphylococcus aureus and escherichia coli, see fig. 5.
Fig. 5 shows the results of the test of the antibacterial rate of the composite film against escherichia coli and staphylococcus aureus, and it can be seen from the figure that the addition of ACS significantly improves the antibacterial rate of PVA/ACS composite film compared with PVA film, and the inhibition rates against escherichia coli and staphylococcus aureus are 44% and 39%, respectively, which are caused by electrostatic interaction between positively charged guanidine groups on ACS and negative charges on bacterial surfaces. The antibacterial rate of the composite film is improved along with the increase of the ACS@ZnO content, wherein when the ACS@ZnO content is 3%, the inhibition rate of the composite film to escherichia coli and staphylococcus aureus is 71% and 70% respectively. The antibacterial mechanism of ZnO nanoparticles is not clearly defined at present, and the most convincing mechanism is that nano zinc oxide generates Reactive Oxygen Species (ROS) under illumination, including H 2 O 2 Radical of hydroxy radical (OH) - ) And superoxide anions, and Zn 2+ Which may lead to bacterial death. ResultsThe PVA/ACS/ZnO composite film has good antibacterial effect on gram-positive bacteria and gram-negative bacteria.
Claims (7)
1. The preparation method of the composite film added with the argininized chitosan and the zinc oxide nano particles is characterized by comprising the following steps:
(1) 1-2 g of chitosan is weighed and dissolved in 50-100 mL MES buffer solution, and the solution is stirred on a magnetic stirrer for 1h until the chitosan is completely dissolved, and is in a transparent state;
(2) 1-3 g of arginine is weighed and dissolved in 50-100 mL of MES buffer solution, and the mixture is stirred on a magnetic stirrer for 5 min until the arginine is completely dissolved;
(3) 1-5 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide EDC and 1-4 g of N-hydroxysuccinimide NHS are weighed and added into the arginine solution in the step (2), and the mixture is stirred and activated on a magnetic stirrer for 2 hours to obtain an activated arginine solution;
(4) Dripping the arginine solution activated in the step (3) into chitosan solution, heating to 45 ℃ in a magnetic stirrer, stirring for 12-24 hours, dialyzing 3 d in deionized water after the reaction is finished, and freeze-drying 48 h to obtain arginine chitosan ACS;
(5) Weighing 0.5-1 g of the arginate chitosan synthesized in the step (4), dissolving in deionized water, heating to 70 ℃ in a magnetic stirrer, and stirring for 0.5-1 h until the arginate chitosan is completely dissolved;
(6) Weighing 1-2 g Zn (NO) 3 ) 2 •6H 2 Adding O into the arginized chitosan water solution in the step (5) and stirring for 30 min;
(7) Dropwise adding 50-100 mL of 0.2M NaOH solution into the solution obtained in the step (6), and stirring for 2h;
(8) Centrifuging the stirred solution obtained in the step (7), washing with deionized water for 3 times, and drying 24 and h in a 50 ℃ oven to obtain ACS@ZnO nano particles;
(9) 1-5 g PVA is weighed and dissolved in 10-50 mL deionized water, and the solution is heated to 95 ℃ and stirred for 2h until the solution is transparent;
(10) Weighing 1-2 g of the arginate chitosan prepared in the step (4), dissolving in 100-200 mL of deionized water, and stirring for 30min at normal temperature until the arginate chitosan is dissolved;
(11) Dropwise adding the arginized chitosan aqueous solution in the step (10) into the PVA aqueous solution in the step (9), and stirring for 2h;
(12) And (3) adding ACS@ZnO nano particles in the step (8) into the mixed aqueous solution prepared in the step (11), performing ultrasonic dispersion for 30min, and preparing a composite film by a tape casting method.
2. The method for preparing the composite film added with arginate chitosan and zinc oxide nano particles according to claim 1, which is characterized in that: the MES buffer was 25 mM at a concentration of 4 < pH < 6.
3. The method for preparing the composite film added with arginate chitosan and zinc oxide nano particles according to claim 1, which is characterized in that: in the step (11), the volume ratio of the PVA aqueous solution to the arginate chitosan aqueous solution is 1:1-4:1.
4. The method for preparing the composite film added with arginate chitosan and zinc oxide nano particles according to claim 1, which is characterized in that: in the step (12), ACS@ZnO nano particles account for 1-5% of the mass of the mixed aqueous solution.
5. The method for preparing the composite film added with arginate chitosan and zinc oxide nano particles according to claim 1, which is characterized in that: the stirring rate was 2000rpm.
6. The method for preparing the composite film added with arginate chitosan and zinc oxide nano particles according to claim 1, which is characterized in that: the power of the ultrasonic probe is 200-500W, the ultrasonic is carried out for 3s, and the interval is 2s.
7. The preparation method of the composite film added with arginate chitosan and zinc oxide nano particles according to any one of claims 1-6, which is characterized by comprising the following specific steps:
(1) Weighing 1 g chitosan, dissolving in 100 mL MES buffer solution, and stirring on a magnetic stirrer for 1h until the chitosan is completely dissolved, wherein the solution is in a transparent state;
(2) Weighing 2.06, g arginine to dissolve in MES buffer solution of 50, mL, and stirring on a magnetic stirrer for 5 min until the arginine is completely dissolved;
(3) 3.4 g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide EDC and 2.04 g of N-hydroxysuccinimide NHS are weighed and added into the arginine solution, and stirred and activated for 2 hours on a magnetic stirrer;
(4) Dripping the activated arginine solution into chitosan solution, heating to 45 ℃ in a magnetic stirrer, and stirring for 12h;
(5) Weighing 0.5g of arginate chitosan, dissolving in 50mL of deionized water, heating to 70 ℃ in a magnetic stirrer, and stirring for 1h until the arginate chitosan is completely dissolved;
(6) 1.487g Zn (NO) was weighed out 3 ) 2 •6H 2 Adding O into the arginized chitosan solution, stirring for 30min, then dropwise adding 50mL of 0.2M NaOH solution, stirring for 2h, centrifuging, washing, and drying in a 50 ℃ oven for 24h to obtain ACS@ZnO nanoparticles;
(7) Adding an argininized chitosan solution into a PVA solution by taking PVA as a matrix and the volume ratio of the argininized chitosan solution to the PVA aqueous solution is 1:2, and stirring the mixed solution on a magnetic stirrer for 1h to be uniform; adding ACS@ZnO nano particles with the mass percentage of 1% -5% into the mixed solution, performing ultrasonic dispersion for 30min, and preparing the composite film with different ACS@ZnO nano particle contents by a tape casting method.
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| DE10163256A1 (en) * | 2001-12-21 | 2003-07-10 | Henkel Kgaa | Surface modified zinc oxide for the production of nanoparticulate dispersions |
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| CN109294003A (en) * | 2018-09-03 | 2019-02-01 | 太原理工大学 | A kind of chitosan containing ZnO/sodium alginate antimicrobial preservative film and preparation method thereof |
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